US3509086A - Epoxy acrylic sealer compositions - Google Patents

Epoxy acrylic sealer compositions Download PDF

Info

Publication number
US3509086A
US3509086A US823940A US3509086DA US3509086A US 3509086 A US3509086 A US 3509086A US 823940 A US823940 A US 823940A US 3509086D A US3509086D A US 3509086DA US 3509086 A US3509086 A US 3509086A
Authority
US
United States
Prior art keywords
methacrylate
sealer
methyl methacrylate
polymer
copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US823940A
Other languages
English (en)
Inventor
Frank Rohrbacher Jr
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Application granted granted Critical
Publication of US3509086A publication Critical patent/US3509086A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S525/93—Reaction product of a polyhydric phenol and epichlorohydrin or diepoxide, having a molecular weight of over 5,000, e.g. phenoxy resins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31529—Next to metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y10T428/31797—Next to addition polymer from unsaturated monomers

Definitions

  • compositions are useful for bonding organic coatings such as methyl methacrylate to organic and metallic substrates.
  • This invention relates broadly to film-forming compositions and more particularly to sealer compositions.
  • sealer compositions are well known in the prior art, previously it has been difiicult or impossible to provide a sealer composition which retained its chip-resistance properties over broad temperature ranges and particularly at low temperatures of around F. Chip-resistance is the ability of a finish coating to withstand impact without chipping away from the substrate. In the automotive industry, this is particularly a problem because of the chipping away of automobile finishes caused by the frequent impacts from road pebbles, etc.
  • sealer composition which comprises a polymeric binder dissolved in an organic solvent, the polymeric binde'r comprising the following components:
  • the sum of the high molecular weight epoxy resin and the adhesion-promoting acrylic polymer is always equal to 100 parts by weight.
  • sealer compositions of this invention provide excellent chip resistance for coatings applied to substrates over wide temperature variations. Another advantage is that the sealer compositions of this invention provide in general stronger bonds than prior art compositions between the substrate and coating they are joining. The sealer compositions of this invention also exhibit improved corrosion resistance properties over the compositions of the prior art.
  • the epoxy resins useful for the sealer compositions of 3,509,086 Patented Apr. 28, 1970 ice this invention are high in molecular weight. In general, they have the structural formula,
  • R as shown above, can be a bisphenol A or a bisphenol F, both of which can be substituted.
  • Suitable substituents include C to C alkyls, halogens such as chlorine, bromine, and fluorine, and C to C alkoxy groups.
  • the preferred epoxy resin is epichlorohydrin-bisphenol A which has the structural formula,
  • E-pichlorohydrin-bisphenol A polymers suitable for use with this invention are commercially available from (1) Dow Chemical Co., (2) Union Carbide Corp., (3) Shell Chemical Co., under the respective trademarks or trade names: (a) D.E.R. 686-EK40 Epoxy Resin, D.E.R. 684EK40 Epoxy Resin, CX-7090 Low Molecular Weight Epoxy Resin; (b) Phenoxy PKHH; and (c) Eponol 55-B40.
  • epichlorohydrin-bisphenol P which has the structural formula
  • n is as defined above.
  • Epoxy resins used with this invention must be high enough in molecular weight so that the films formed are flexible and non-brittle; molecular weights of about 20,000 are generally suflicient. Higher molecular weights are preferred up to and beyond 200,000. It is understood, however, that epoxy resins having molecular weights as low as 15,000 can be used in some embodiments of this invention.
  • the high molecular weight epoxy resins constitute from about 50 to about of the polymeric binder; the balance being the acrylic polymer. Amounts lower than 50% usually do not sufficiently retain the tough physical and chemical properties exhibited by high molecular weight epoxies. Amounts in excess of 95% usually do not exhibit the high amount of adhesion gained by increasing the amount of acrylic.
  • Acrylic polymers useful for this invention must be adhesion-promoting.
  • the adhesion-promoting qualities are gained by the incorporation in the polymer chain of monomeric units which cause the polymer resin to exhibit good adhesion properties towards a substrate such as an alkyd resin.
  • adhesion-promoting acrylic polymers suitable for use with this invention:
  • 80/ 14/ 1 four component polymer of methyl methacrylate/ 3-(2-rnethacryloxyethyl -2,2-spirocyclohexyl oxazolidine/butyl acrylate/t-butyl amino ethyl methacrylate;
  • copolymer is used herein to designate multicomponent polymers which include any combination of the various monomeric units, e.g., terpolymers, 4-component polymers, S-component polymers, etc.
  • 'Ihus copolymers of the adhesion-promoting acrylic polymers would include any polymers containing two or more of the required monomeric units, such as methyl methacrylate, 3-(2-methacryloxyethyl) 2,2-spirocyclohexyl oxazolidine and t-butyl amino ethyl methacrylate.
  • monomers can be substituted for some or all of the methyl methacrylate in the above examples.
  • These monomers include esters of acrylic acid or methacrylic acid with alcohols having from 1 to 18 carbon atoms such as methyl acrylate or methacrylate, ethyl acrylate or methacrylate, propyl acrylate or methacrylate, isopropyl acrylate or methacrylate, the various butyl acrylates or methacrylates, cyclohexyl acrylate or methacrylate, berTzyl acrylate or methacrylate, phenyl acrylate or methacrylate, n-hexyl, n-octyl, t-octyl, dodecyl, hexadecyl, or octadecyl acrylates or methacrylates, acrylonitrile, methacrylonitrile, acrylarnide, methacrylamid, styrene,
  • 3-amino 3-hydroxy propyl methacrylate is prepared by reacting methacrylic acid with 2(1-aziridinyl) ethanol.
  • Z-amino propyl methacrylate and 2-amino ethyl methacrylate are prepared by reacting methacrylic acid with ethylene imine and propylene imine respectively.
  • the molecular weights of the adhesion-promoting acrylic polymers in general range from about 30 ,000 to about 150,000.
  • the preferred range is 50,000 to 75,000 because they have good viscosity properties in this range.
  • the preferred acrylic polymer is a 95/5 copolymer of methyl methacrylate and 3-(2-methacryloxyethyl)-2,2- spirocyclohexyl oxazolidine. This copolymer is preferred because it is commercially available, economical, and results in a high level of adhesion in the sealer composition.
  • a second preferred acrylic polymer is a 84/ 15/ 1 threecomponent polymer of methyl methacrylate/3-(2-methacryloxyethyl) 2,2 spirocyclohexyl oxazolidine/t-butyl amino ethyl methacrylate.
  • This particular acrylic polymer is preferred because it results in sealer compositions having highly uniform adhesion characteristics.
  • sealer compositions prepared from this polymer form clear, noncloudy films which are evidence of unusually good compatibility between the epoxy and acrylic components.
  • Solvents preferred for this invention are glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether, etc.
  • other organic solvents can be used in combination with these preferred solvents including: aromatic hydrocarbons such as toluene, xylene, substituted benzenes, and other analogues; alcohols such as methanol, ethanol, propanol and butanol; ketones such as methly ethyl ketone, acetone, diethyl ketone and methyl isobutyl ketone. Methyl ethyl ketone with about 2% Water also can be used.
  • the sealer compositions of this invention can contain other additives such as pigments, plasticizers, surfactants, diluents, etc. Pigmentation of up to about 30% pigment volume concentration is often desirable. Suitable examples of pigments include titanium dioxide, aluminum silicate, talc, carbon black, zinc, barium or strontium chromates, calcium carbonate, etc.
  • Plasticizers such as butyl benyl phthalate can be added to improve flexibility.
  • diluent resins suitable for use in these compositions are low molecular weight epoxies, short oil epoxy esters, non-adhesion-promoting acrylics, polystyrenes, vinyl polymers, etc.
  • Diluent liquids such as toluene, xylene, acetone, etc., can also be used.
  • Formula 1 Mill base Parts Aluminum silicate 19.49 Carbon black 0.78 Titanium dioxide 19.61
  • the above composition is premixed and run through a sand mill to a fineness of 0.5 mil.
  • Formula 2 is then reduced to spray for conventional air spray equipment, manual or automatic, with a 200% by volume add of a solvent composed of 72% acetone and 28% toluene.
  • Substrates are prepared by dipping 4" x 12", 20 gauge steel panels in an automotive high bake sheet metal primer (approximate composition25% pigment volume, 94/ 650% oil length Soya alkyl/liquid epoxy resin). The primer is reduced such that 0.25 mil of primer is deposited 6" from the top of the panel after a bake of 30 minutes at 400 F.
  • the reduced composition of Formula 2 is spray applied to the above substrate to a film build of 0.15 to 0.25 mil. After a flash period of 1 minute, 2.5 mils of conventional acrylic lacquer topcoat is applied wet on wet and baked 30 minutes at 285 F.
  • Sealer Rating Formula 2 8-9 No sealer 0 Sealer formulated with no methyl methacrylate and 3-(2-methacryloxyethyl)-2, 2-spirocyclohexyl oxazolidine polymer Sealer formulated with no epoxy -6 TEST PROCEDURE FOR 0 F. GRAVELOMETER CHIP TEST The test is conducted in at 0 F. normal atmosphere.
  • the Gravelometer consists of a device to hold a 4 in. X 12 in. test panel. A 2 in. horizontal air line fitted with a valve capable of supplying compressed air at at least 75 psi. when the valve is wide open. The opened end of the air line is 8 in. from the test panel and pointed directly at it.
  • the air line is fitted with a vertical 2 in. pipe 8 in. behind its opened end.
  • the vertical pipe is 18 in. high with the upper end flared and fitted with a plug to accept 1 pint of gravel in. to /8 in. in size.
  • a 4 in. x 12 in. test panel is prepared. It is allowed to cool to 0 F. for a minimum of 2 hours. It is then placed in the holding device and the air valve is open to a dynamic pressure of 75 psi. Then the stopper is pulled from the flared end of the vertical pipe allowing 1 pint of gravel to fall into the moving air stream. As the gravel falls into the air stream it is projected at high velocity into the test panel.
  • Example I-B Results similar to those described in Example I-A are obtained following the procedure of Example I-A except that the methyl methacrylate and 3-(2-methacryloxyethyl) -2,2-spirocyclohexyl oxazolidine-95/5 polymer is replaced by a methyl methacrylate/hydroxy amino propyl methacrylate-98/ 2 polymer.
  • Example I-C Results similar to those described in Example I-A are obtained by following the procedure of Example I-A except that the methyl methacrylate/3-(2-methacryloxyethyl)-2,2-spirocyclohexyl oxazolidine-955 polymer is replaced by a methyl methacrylate/ 3 (Z-methacryloxyethyl)-2,2-spirocyclohexyl oxazolidine-SS/ 15 polymer.
  • EXAMPLE I-E Substrates are prepared by sanding 4" x 12", 20 guage automotive steel with 400 sand paper.
  • the reduced sealer of Formula 2 is spray applied to a film build of 0.2 mil with appropriate controls and topcoated and baked as in Example I-A.
  • the following chip results are obtained:
  • Sealer Rating Formula 2 10 No sealer 2 Sealer formulated with no methyl methacrylate/ 3-(2-methacryloxyethyl) 2,2-spirocyclohexyl oxazolidine polymer 10 Sealer formulated with no epoxy 4 EXAMPLE II Substrates are prepared by electrodepositing on 4" x 12" steel panels a malenized linseed oil sheet metal primer (approximate composition 10% pigment volume, 200 Acid Number malenized linseed oil thatwas neutralized with dimethylethanol amine and reduced to 10% solids in water) at 75 volts for one minute and baking 30 minutes at 390 F. The substrates were sealed and topcoated as in Example I.
  • Sealer Rating Formula 2 9 No sealer 2 Sealer formulated with no copolymer of methyl methacrylate and 3 (2 -methacryloxyethyl)- 2,2-spirocyclohexyl oxazolidine 95/5 0 Sealer formulated with no epoxy 6 EXAMPLE III Examples of clear automotive sealers are prepared as follows:
  • Each of the above clears can be diluted for spray with 200% addition of a 50/ 30/20-acetone/ethylene glycol monoethyl ether/toluene blend.
  • Substrates are prepared as in Example I-A using a black sheet metal primer with an approximate composition of 8/ 7 Tofa alkyl/liquid epoxy/urea formaldehyde lbinder at 25% pigment volume and baked at 30 minutes at 425 F.
  • the substrates are prepared in the same manner as Example 1 and the reduced composition is applied to the substrate to a film build of about 0.5 mil. After a flush period of 1 minute, 2.0 to 2.2 mils of a conventional acrylic laquer topcoat is applied wet on wet and the substrate is baked for 30 minutes at 285 F.
  • Chip resistance values are at least as good as those reported in Example I and in many instances are even better than those reported in Example I.
  • films cast from the sealer composition are clear and tough rather than cloudy (which is illustrative of phase separation in the composition and is often typical in epoxy-acrylic blends).
  • the sealer composition exhibits an unusually high uniformity in adhesion to the automotive acrylic laquer topcoats and high bake alkyd, epoxy and/ or epoxy ester primers.
  • Example IV The procedures of Example IV are repeated except that the 84/15/1 copolymer of Example IV is replaced with the following copolymers:
  • Example V.80/14/5/l four-component polymer of methyl methacrylate/ 3 (2-methacryloxyethyl)-2,2-spirocyclohexyl oxazolidine/butyl acrylate/t-butyl amino ethyl methacrylate.
  • Example VII The procedures of Example IV are repeated except that a low molecular weight epoxy resin (CX-7090 available from Dow Chemical Co. and reported to have a molecular weight of about 15,000 to 20,000) is used in place of the 200,000 molecular weight epichlorohydrinbisphenol A polymer.
  • CX-7090 available from Dow Chemical Co. and reported to have a molecular weight of about 15,000 to 20,000
  • the sealer compositions produced exhibit properties similar to those of Example I.
  • the coating compositions of this invention are useful as sealers particularly for providing adhesion between coatings such as acrylic lacquer topcoats to coatings such as alkyd resins, epoxy esters and oils which traditionally are non-adhesive to each other. These compositions are also useful for bonding topcoats or other organic films to such substrates as metal, Fiberglas, rubber, glass, wood, plastics, cotton and other fabrics, and other organic substrates. These are particularly useful for bonding acrylic automotive topcoats to high baked sheet metal primers. These are also useful for bonding decorative enamel finishes such as are found on household appliances to metal or other organic substrates. Another use is in bonding an automotive topcoat to metals, particularly bright metals such as chrome, bright aluminum and stainless steel.
  • a sealer composition which comprises a polymeric binder dissolved in an organic solvent, said polymeric binder comprising the following components:
  • n is an integer sufiicient to provide the epoxy resin with a molecular weight of at least about 20,000;
  • R is a divalent aromatic radical selected from the group of bisphenol A, substituted bisphenol A, bisphenol F and susbtituted bisphenol E;
  • R is a C to C alkyl; and
  • R R and R are individually selected from the group of hydrogen and a C to C alkyl;
  • an adhesion-promoting acrylic polymer is a copolymer containing monomeric units selected from
  • a sealer composition of claim 1 wherein the adhesion-promoting acrylic polymer is a copolymer containing three monomeric units in which two of the monomeric units are 3-(Z-methacryloxyethyl)-2,2-spirocyclohexyl oxazolidine and t-butyl aminoethyl methacrylate.
  • a sealer composition of claim 2 wherein the adhesion-promoting polymer is a coplymer formed from about 84 parts of methyl methacrylate, about 15 parts of 3-(2- methacryloxy-ethyl)-2,2-spirocyclohexyl oxazolidine and about 1 part of t-butyl amino ethyl methacrylate.
  • a sealer composition of claim 1 wherein the (A) high molecular Weight epoxy resin is epichlorohydrinbisphenol a polymer having a molecular weight of from about 20,000 to about 200,000.
  • a sealer composition of claim 5 wherein the adhesion-promoting polymer is a copolymer formed from about parts of methyl methacrylate and about 5 parts of 3-(Z-methacryloxy-ethyl)-2,2-spiro-cyclohexyl oxazolidine.
  • a sealer composition of claim 8 which contains pigmentation in an amount of up to about 40% pigment volume concentration.
  • a sealer composition of claim 11 wherein the total pigmentation comprises about 49% titanium dioxide, about 49% aluminum silicate and about 2% carbon black; the total pigmentation being present in an amount of about 10% pigment vo-lume concentration.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Sealing Material Composition (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US823940A 1967-06-30 1969-05-12 Epoxy acrylic sealer compositions Expired - Lifetime US3509086A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US65019767A 1967-06-30 1967-06-30

Publications (1)

Publication Number Publication Date
US3509086A true US3509086A (en) 1970-04-28

Family

ID=24607886

Family Applications (1)

Application Number Title Priority Date Filing Date
US823940A Expired - Lifetime US3509086A (en) 1967-06-30 1969-05-12 Epoxy acrylic sealer compositions

Country Status (7)

Country Link
US (1) US3509086A (en:Method)
BE (1) BE717360A (en:Method)
CH (1) CH527261A (en:Method)
DE (1) DE1769675A1 (en:Method)
FR (1) FR1570348A (en:Method)
GB (1) GB1176108A (en:Method)
SE (1) SE351671B (en:Method)

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3157775A (en) * 1961-05-03 1964-11-17 Pyrometrics Inc Radiant heater
US3819567A (en) * 1971-12-03 1974-06-25 Du Pont Sealer composition of an acrylic-epoxy ester graft copolymer and an epoxy resin
US3819447A (en) * 1971-06-07 1974-06-25 Reichhold Albert Chemie Ag Process for gluing solid materials
US3945963A (en) * 1974-01-07 1976-03-23 Ppg Industries, Inc. Water-based epoxy acrylic coating compositions
US4042539A (en) * 1973-04-12 1977-08-16 E. I. Du Pont De Nemours And Company Primer-surfacer composition of an acrylic polymer, a polyester resin and an organic dispersant
US4105613A (en) * 1976-08-16 1978-08-08 The Dexter Corporation Epoxy hydroxol primer
US4111870A (en) * 1977-05-24 1978-09-05 E. I. Du Pont De Nemours And Company Primer composition of an acrylic epoxy ester graft copolymer, a high molecular weight epoxy resin and a heat reactive condensate
US4129610A (en) * 1975-10-23 1978-12-12 Hitachi Chemical Co., Ltd. Water-soluble coating composition for ship bottoms
US4294939A (en) * 1978-06-15 1981-10-13 Toray Industries, Inc. Coating composition
US4303760A (en) * 1978-07-15 1981-12-01 Sony Corporation Adhesive
US4335829A (en) * 1978-11-29 1982-06-22 Ppg Industries, Inc. Coated metal surfaces and method of coating metal surfaces with aqueous resinous dispersions of epoxy resins and acrylic polymers
US4362770A (en) * 1981-04-02 1982-12-07 The Sherwin-Williams Company Nitrocellulose-free primer-surfacer
US4375489A (en) * 1981-04-03 1983-03-01 Shell Oil Company Vinyl ester polymer concrete compositions comprising fly ash
US4499216A (en) * 1983-07-05 1985-02-12 Hitco Method and resin solution for splicing carbonized polyacrylonitrile material
US4503174A (en) * 1983-09-06 1985-03-05 E. I. Du Pont De Nemours And Company Low temperature curing coating composition
US4514468A (en) * 1983-05-26 1985-04-30 Sprague Electric Company Electronic component with UV-cured coating
US4522966A (en) * 1980-05-29 1985-06-11 Nippon Sheet Glass Co., Ltd. Non-fogging coating composition and a shaped article coated therewith
US4525521A (en) * 1983-10-14 1985-06-25 E. I. Du Pont De Nemours And Company Coating composition of an acrylic polymer having amino ester groups and a glycidyl acrylic polymer
US4609692A (en) * 1984-11-28 1986-09-02 E. I. Du Pont De Nemours And Company Low temperature curing maintenance coatings comprising (a) epoxy resin (b) polyamine curing agent (c) polymer containing pendant aminoester groups and (d) organic solvent
USRE32272E (en) * 1980-05-29 1986-10-28 Sumitomo Chemical Company, Limited Non-fogging coating composition and a shaped article coated therewith
US4699936A (en) * 1986-02-27 1987-10-13 E. I. Du Pont De Nemours And Company Coating composition of an amine polymer and an epoxy resin
US4816500A (en) * 1985-11-25 1989-03-28 E. I. Du Pont De Nemours And Company Two component coating composition of an anhydride containing polymer and a glycidyl component
AU585842B2 (en) * 1983-10-14 1989-06-29 E.I. Du Pont De Nemours And Company Coating composition of an acrylic polymer having amino ester groups and a glycidyl acrylic polymer
US5025068A (en) * 1986-04-14 1991-06-18 Hughes Aircraft Company Reacting novolac and bisphenol F epoxy resins with carboxy-terminated butadiene-acrylonitrile
US5057555A (en) * 1988-06-27 1991-10-15 White Donald A Multi-component coating composition comprising an anhydride containing polymer, a glycidyl component and a polymer with multiple hydroxyl groups
US5093391A (en) * 1988-06-27 1992-03-03 E. I. Du Pont De Nemours And Company Multi-component coating composition comprising an anhydride containing polymer, a glycidyl component and an acid functional component
WO1999039179A1 (en) * 1998-01-28 1999-08-05 Q-Panel Lab Products Multi-test gravelometer
US6679095B1 (en) 1998-01-28 2004-01-20 Q-Panel Lab Products Corporation Multi-test gravelometer
US20080032154A1 (en) * 2004-07-20 2008-02-07 Yasumasa Akatsuka Epoxy Resin, Epoxy Resin Composition and Cured Product Thereof
US20100062211A1 (en) * 2006-12-13 2010-03-11 Masayuki Kawazoe Epoxy resin composition for fiber reinforced composite material
CN112352026A (zh) * 2018-07-19 2021-02-09 陶氏环球技术有限责任公司 耐候性且耐久性涂料组合物
US20210332274A1 (en) * 2018-09-26 2021-10-28 Dai Nippon Printing Co., Ltd. Adhesive composition and foamable adhesive sheet

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3561017D1 (en) * 1984-02-28 1987-12-23 Shell Int Research Heat-curable polyepoxide-(meth)acrylate ester-styrene composition

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2602075A (en) * 1948-11-26 1952-07-01 Courtaulds Ltd Production of thermoplastic resins and the production from such resins of threads, fibres, filaments, and the like
US2949383A (en) * 1958-05-06 1960-08-16 Du Pont Process of coating with methyl methacrylate composition therefore and article produced thereby
US2949445A (en) * 1958-05-06 1960-08-16 Du Pont Methyl methacrylate polymers containing amino residues
US3177089A (en) * 1961-04-12 1965-04-06 Shell Oil Co Base coated with a linear thermoplastic polyether
US3234313A (en) * 1961-07-03 1966-02-08 Union Carbide Corp Thermoplastic films and process for preparing same
US3238087A (en) * 1962-12-19 1966-03-01 Union Carbide Corp Method of making laminated structural elements and article produced thereby
US3287205A (en) * 1962-09-24 1966-11-22 Union Carbide Corp Low temperature bonding thermoplastic polyhydroxyether adhesive compositions
US3297784A (en) * 1964-12-17 1967-01-10 Union Carbide Corp Alpha olefin polymer modified thermoplastic polyhydroxyether compositions
US3308205A (en) * 1963-08-01 1967-03-07 Union Carbide Corp Thermoplastic polyhydroxyether with nitrile rubber and laminates thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2602075A (en) * 1948-11-26 1952-07-01 Courtaulds Ltd Production of thermoplastic resins and the production from such resins of threads, fibres, filaments, and the like
US2949383A (en) * 1958-05-06 1960-08-16 Du Pont Process of coating with methyl methacrylate composition therefore and article produced thereby
US2949445A (en) * 1958-05-06 1960-08-16 Du Pont Methyl methacrylate polymers containing amino residues
US3177089A (en) * 1961-04-12 1965-04-06 Shell Oil Co Base coated with a linear thermoplastic polyether
US3177090A (en) * 1961-04-12 1965-04-06 Shell Oil Co Base coated with a linear thermoplastic polyether
US3234313A (en) * 1961-07-03 1966-02-08 Union Carbide Corp Thermoplastic films and process for preparing same
US3287205A (en) * 1962-09-24 1966-11-22 Union Carbide Corp Low temperature bonding thermoplastic polyhydroxyether adhesive compositions
US3238087A (en) * 1962-12-19 1966-03-01 Union Carbide Corp Method of making laminated structural elements and article produced thereby
US3308205A (en) * 1963-08-01 1967-03-07 Union Carbide Corp Thermoplastic polyhydroxyether with nitrile rubber and laminates thereof
US3297784A (en) * 1964-12-17 1967-01-10 Union Carbide Corp Alpha olefin polymer modified thermoplastic polyhydroxyether compositions

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3157775A (en) * 1961-05-03 1964-11-17 Pyrometrics Inc Radiant heater
US3819447A (en) * 1971-06-07 1974-06-25 Reichhold Albert Chemie Ag Process for gluing solid materials
US3819567A (en) * 1971-12-03 1974-06-25 Du Pont Sealer composition of an acrylic-epoxy ester graft copolymer and an epoxy resin
US4042539A (en) * 1973-04-12 1977-08-16 E. I. Du Pont De Nemours And Company Primer-surfacer composition of an acrylic polymer, a polyester resin and an organic dispersant
US3945963A (en) * 1974-01-07 1976-03-23 Ppg Industries, Inc. Water-based epoxy acrylic coating compositions
US4129610A (en) * 1975-10-23 1978-12-12 Hitachi Chemical Co., Ltd. Water-soluble coating composition for ship bottoms
US4105613A (en) * 1976-08-16 1978-08-08 The Dexter Corporation Epoxy hydroxol primer
US4111870A (en) * 1977-05-24 1978-09-05 E. I. Du Pont De Nemours And Company Primer composition of an acrylic epoxy ester graft copolymer, a high molecular weight epoxy resin and a heat reactive condensate
US4294939A (en) * 1978-06-15 1981-10-13 Toray Industries, Inc. Coating composition
US4303760A (en) * 1978-07-15 1981-12-01 Sony Corporation Adhesive
US4335829A (en) * 1978-11-29 1982-06-22 Ppg Industries, Inc. Coated metal surfaces and method of coating metal surfaces with aqueous resinous dispersions of epoxy resins and acrylic polymers
US4522966A (en) * 1980-05-29 1985-06-11 Nippon Sheet Glass Co., Ltd. Non-fogging coating composition and a shaped article coated therewith
USRE32272E (en) * 1980-05-29 1986-10-28 Sumitomo Chemical Company, Limited Non-fogging coating composition and a shaped article coated therewith
US4362770A (en) * 1981-04-02 1982-12-07 The Sherwin-Williams Company Nitrocellulose-free primer-surfacer
US4375489A (en) * 1981-04-03 1983-03-01 Shell Oil Company Vinyl ester polymer concrete compositions comprising fly ash
US4514468A (en) * 1983-05-26 1985-04-30 Sprague Electric Company Electronic component with UV-cured coating
US4499216A (en) * 1983-07-05 1985-02-12 Hitco Method and resin solution for splicing carbonized polyacrylonitrile material
US4503174A (en) * 1983-09-06 1985-03-05 E. I. Du Pont De Nemours And Company Low temperature curing coating composition
AU585842B2 (en) * 1983-10-14 1989-06-29 E.I. Du Pont De Nemours And Company Coating composition of an acrylic polymer having amino ester groups and a glycidyl acrylic polymer
US4525521A (en) * 1983-10-14 1985-06-25 E. I. Du Pont De Nemours And Company Coating composition of an acrylic polymer having amino ester groups and a glycidyl acrylic polymer
US4609692A (en) * 1984-11-28 1986-09-02 E. I. Du Pont De Nemours And Company Low temperature curing maintenance coatings comprising (a) epoxy resin (b) polyamine curing agent (c) polymer containing pendant aminoester groups and (d) organic solvent
US4816500A (en) * 1985-11-25 1989-03-28 E. I. Du Pont De Nemours And Company Two component coating composition of an anhydride containing polymer and a glycidyl component
US4699936A (en) * 1986-02-27 1987-10-13 E. I. Du Pont De Nemours And Company Coating composition of an amine polymer and an epoxy resin
US5025068A (en) * 1986-04-14 1991-06-18 Hughes Aircraft Company Reacting novolac and bisphenol F epoxy resins with carboxy-terminated butadiene-acrylonitrile
US5093391A (en) * 1988-06-27 1992-03-03 E. I. Du Pont De Nemours And Company Multi-component coating composition comprising an anhydride containing polymer, a glycidyl component and an acid functional component
US5057555A (en) * 1988-06-27 1991-10-15 White Donald A Multi-component coating composition comprising an anhydride containing polymer, a glycidyl component and a polymer with multiple hydroxyl groups
WO1999039179A1 (en) * 1998-01-28 1999-08-05 Q-Panel Lab Products Multi-test gravelometer
US6679095B1 (en) 1998-01-28 2004-01-20 Q-Panel Lab Products Corporation Multi-test gravelometer
US20080032154A1 (en) * 2004-07-20 2008-02-07 Yasumasa Akatsuka Epoxy Resin, Epoxy Resin Composition and Cured Product Thereof
US20100062211A1 (en) * 2006-12-13 2010-03-11 Masayuki Kawazoe Epoxy resin composition for fiber reinforced composite material
US8668983B2 (en) * 2006-12-13 2014-03-11 The Yokohama Rubber Co., Ltd. Epoxy resin composition for fiber reinforced composite material
CN112352026A (zh) * 2018-07-19 2021-02-09 陶氏环球技术有限责任公司 耐候性且耐久性涂料组合物
US20210332274A1 (en) * 2018-09-26 2021-10-28 Dai Nippon Printing Co., Ltd. Adhesive composition and foamable adhesive sheet

Also Published As

Publication number Publication date
CH527261A (de) 1972-08-31
FR1570348A (en:Method) 1969-06-06
SE351671B (en:Method) 1972-12-04
BE717360A (en:Method) 1968-12-30
DE1769675A1 (de) 1971-10-28
GB1176108A (en) 1970-01-01

Similar Documents

Publication Publication Date Title
US3509086A (en) Epoxy acrylic sealer compositions
US4177178A (en) Thermosetting acrylic copolymer compositions
CA1279743C (en) Water dilutable coating compositions for base coats for wet-on-wet application of clear coat on base coat
US3705076A (en) Adhesive composition and laminating process
US3222418A (en) Curable coating composition comprising carboxyl containing copolymer, a second copolymer and amine/aldehyde condensate or epoxy resin
EP0136842A2 (en) Low temperature curing coating composition
GB2247632A (en) Two-layer coatings
CA1067236A (en) Aqueous acrylic-carboxylated polyether compositions
US3637546A (en) Thermosetting acrylic enamel containing cellulose acetate butyrate
US3505269A (en) Epoxy acrylic coating composition modified with a trialkoxysilane
US3819567A (en) Sealer composition of an acrylic-epoxy ester graft copolymer and an epoxy resin
KR20010013787A (ko) 도료용 수지조성물
GB2169911A (en) Acrylic resin for use in high solids paints
US5880187A (en) Top coating compositions
US3816557A (en) Sealer composition of an acrylic-epoxy ester graft copolymer and an epoxy resin
US5073602A (en) Thermosetting resin composition
EP0103118A1 (en) High solids primer-guidecoats based on t-butyl acrylate and styrene
JPH06248233A (ja) 硬化性組成物
US3627779A (en) Sealer or primer composition of an acrylic polymer having adhesion promoting groups and an epoxy resin
US3231410A (en) Graft copolymer composition, method of coating therewith and resultant article
US4178318A (en) Graft polybutadiene copolymers
US3812067A (en) Stoving lacquers
US4515835A (en) High solids thermosetting coating compositions, cured coatings, coated articles, and processes
US4864000A (en) Thermosetting compositions comprising acrylic polymers which are substantially free of active hydrogens
EP0775175A1 (en) Water-dispersible acrylic graft copolymer, method for making it and water-based paint